CN105749339B - A kind of three-dimensional cross-linked macropore bracket of nylon nano fiber and preparation method thereof - Google Patents
A kind of three-dimensional cross-linked macropore bracket of nylon nano fiber and preparation method thereof Download PDFInfo
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- CN105749339B CN105749339B CN201610108622.5A CN201610108622A CN105749339B CN 105749339 B CN105749339 B CN 105749339B CN 201610108622 A CN201610108622 A CN 201610108622A CN 105749339 B CN105749339 B CN 105749339B
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- 229920001778 nylon Polymers 0.000 title claims abstract description 41
- 239000004677 Nylon Substances 0.000 title claims abstract description 32
- 239000002121 nanofiber Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000000835 fiber Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000004088 foaming agent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 9
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 9
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 238000007710 freezing Methods 0.000 claims abstract description 3
- 230000008014 freezing Effects 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 210000000056 organ Anatomy 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 210000000601 blood cell Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Textile Engineering (AREA)
- Dermatology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The present invention relates to three-dimensional cross-linked macropore brackets of a kind of nylon nano fiber and preparation method thereof, it is using electrostatic spinning nano nylon fiber film under certain condition, and by tunica fibrosa in water high speed shear at staple fiber, after dividing sample, a certain size crystal calcium carbonate particle is added as pore-foaming agent, freeze-dried molding removes calcium carbonate pore-foaming agent with dilute hydrochloric acid, it is crosslinked after washing with polyacrylic acid solution, then obtains the three-dimensional cross-linked macropore bracket of nylon nano fiber through washing, freezing and freeze-drying.The bracket has macropore, grows into suitable for cell with what is organized.Nylon fiber is well bonded between fiber after polyacrylic acid crosslinked, and bracket is integrated with preferable elasticity and overall structure stability, can be used for the reparation of tissue and organ.
Description
Technical field
The present invention relates to three-dimensional cross-linked macropore brackets of a kind of nylon nano fiber and preparation method thereof, belong to bio-medical material
Expect technical field.
Background technique
Nylon is the thermoplastic resin general name for containing recurring amide radical group-[NHCO]-on molecular backbone, it has good power
Performance, heat resistance, wear resistance, chemical resistance and self-lubrication are learned, and coefficient of friction is low, has certain anti-flammability, easily
In processing, it is suitable for using glass fibre and other filler filling enhancing modifieds, is widely used in the industry.Nylon is at present in life
Object Material Field is also widely used, can be made into timbering material of various shapes for the organs such as bone, skin and heart and
The reparation (Suman Das etc., 2003, Rapid Prototyping Journal, 9(1) of tissue: 43-49).In the bracket,
Solid construction is generally all made in nylon, and the less fibrous framework that porous network shape is made is difficult to cell, blood vessel and nerve etc.
Internal stent growth.Nylon can be spun to the fiber of various scales, but due to, without binding force, inciting somebody to action between nylon fiber in industry
The fibrous framework that three-dimensional porous network shape is made in nylon fiber is very difficult.
Summary of the invention
Main imagination of the invention is to prepare nano-nylon film using the method for electrostatic spinning, in water by nylon film
High speed shear obtains the suspension of nylon nano fiber at staple fiber, and after dividing suspension to sample, a certain size crystal carbonic acid is added
Calcium pore-foaming agent, freeze-dried molding remove calcium carbonate pore-foaming agent with dilute hydrochloric acid, are crosslinked after washing with polyacrylic acid solution, then
The three-dimensional cross-linked macropore bracket of nylon nano fiber is obtained through washing, freezing and freeze-drying.
The preparation method of the three-dimensional cross-linked macropore bracket of nylon nano fiber is described in detail below in the present invention.
(1) electrostatic spinning nano nylon fiber film, prepares certain density nylon solution, and solvent is that formic acid and water mix
Object passes to certain spinning voltage electrostatic spinning and forms nano-nylon tunica fibrosa.
(2) a certain amount of nano-nylon tunica fibrosa is weighed, is added in quantitative water, high speed shear is at short fibre in water
Dimension.
(3) divide sample into weighing bottle, crystal calcium carbonate pore-foaming agent of the average particle size between 200~500 μm is added ,-
It freeze forming and is lyophilized at 18 DEG C.
(4) sample after being lyophilized removes calcium carbonate pore-foaming agent with dilute hydrochloric acid, is handed over again with 10% polyacrylic acid solution after washing
Connection.
(5) bracket after being crosslinked is through washing, freeze forming at -18 DEG C, is freeze-dried and can get nylon nano fiber three-dimensional
Crosslinked Macroporous bracket.
The three-dimensional cross-linked macropore bracket of nylon nano fiber produced by the present invention is white disk, and shape and height can divide
Different containers is used in sample and sample volume is divided to adjust.The diameter of nylon nano fiber can pass through the technique item of change electrostatic spinning
Part is adjusted, and bracket has macroporous structure, and nylon fiber is well bonded between fiber after polyacrylic acid crosslinked, bracket
It is integrated with preferable elasticity and overall structure stability, can be used for the reparation of tissue and organ.The preparation process is simple, compared to
Simple method of electrostatic spinning, the method can easily prepare the bracket of three-dimensional structure.
Specific embodiment
Combined with specific embodiments below, the content of present invention is further described, but implementation of the invention is not
It is confined to this.
Embodiment 1: taking the formic acid of 9ml and the water of 1ml respectively, is uniformly mixed, and weighs 1.0g nylon 6, and stirring and dissolving is stood
2 hours.6 solution of nylon is added in syringe, the voltage spinning of 15kV is passed to, is collected on the aluminium foil of ground connection, can get
The film of nylon fiber average diameter 80nm.0.5g nano-nylon tunica fibrosa is weighed, cuts into short fibre in 100ml water high speed
Dimension, divides sample into weighing bottle, and the calcium carbonate granule that average particle size is 200 μm is added, highly identical as the liquid level of sample is divided, -18
Freeze forming at DEG C, is lyophilized in freeze dryer.Sample after freeze-drying removes calcium carbonate pore-foaming agent with dilute hydrochloric acid, again sample after washing
Product are immersed in 10% polyacrylic acid solution and are crosslinked, and the time is 2 hours, take out crosslinking bracket, wash, freeze at -18 DEG C,
Being lyophilized again in freeze dryer can get nylon 6/nanometer fibre three-dimensional Crosslinked Macroporous bracket.
Embodiment 2: taking the formic acid of 8ml and the water of 2ml respectively, is uniformly mixed, weighs 2.0g nylon66 fiber, stirring and dissolving is quiet
It sets 2 hours.Nylon66 fiber solution is added in syringe, the voltage spinning of 20kV is passed to, collects on the aluminium foil of ground connection, can obtain
Obtain the film of nylon fiber average diameter 150nm.66 tunica fibrosa of 2.0g nano-nylon is weighed, is cut into 100ml water high speed
Staple fiber divides sample into weighing bottle, and the calcium carbonate granule that average particle size is 500 μm is added, highly identical as the liquid level of sample is divided,
The freeze forming at -18 DEG C, is lyophilized in freeze dryer.Sample after freeze-drying removes calcium carbonate pore-foaming agent with dilute hydrochloric acid, after washing
Sample is immersed in again in 10% polyacrylic acid solution and is crosslinked, the time is 2 hours, takes out crosslinking bracket, washes, cold at -18 DEG C
Freeze, being lyophilized again in freeze dryer can get the three-dimensional cross-linked macropore bracket of nylon66 fiber nanofiber.
Claims (6)
1. a kind of three-dimensional cross-linked macropore bracket of nylon nano fiber, it is characterised in that Electrospun nano-fibers under certain condition
Nylon membrane, by nano-nylon tunica fibrosa, high speed shear is at staple fiber in water, and after dividing sample, the crystal carbon with certain particle size is added
Sour calcium pore-foaming agent, freeze-dried molding remove calcium carbonate pore-foaming agent with dilute hydrochloric acid, are crosslinked after washing with polyacrylic acid solution,
The three-dimensional cross-linked macropore bracket of nylon nano fiber is obtained through washing, freezing and freeze-drying again.
2. the three-dimensional cross-linked macropore bracket of nylon nano fiber according to claim 1, it is characterised in that used nylon
For nylon 6 or nylon66 fiber.
3. the three-dimensional cross-linked macropore bracket of nylon nano fiber according to claim 1, it is characterised in that electrostatic spinning nano
When tunica fibrosa, nylon concentration is 10.0%(w/v) or 20.0%(w/v), mixture of the solvent for formic acid and water, volume ratio 90:
10 or 80:20, spinning voltage are 15kV or 20kV.
4. the three-dimensional cross-linked macropore bracket of nylon nano fiber according to claim 1, it is characterised in that nano-nylon fiber
Concentration when high speed shear is 0.5%(w/v in water) or 2%(w/v).
5. the three-dimensional cross-linked macropore bracket of nylon nano fiber according to claim 1, it is characterised in that the calcium carbonate used
The particle size range of pore-foaming agent is between 200~500 μm.
6. the three-dimensional cross-linked macropore bracket of nylon nano fiber according to claim 1, it is characterised in that the crosslinking agent used
For 10% polyacrylic acid solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610108622.5A CN105749339B (en) | 2016-02-27 | 2016-02-27 | A kind of three-dimensional cross-linked macropore bracket of nylon nano fiber and preparation method thereof |
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|---|---|---|---|
| CN201610108622.5A CN105749339B (en) | 2016-02-27 | 2016-02-27 | A kind of three-dimensional cross-linked macropore bracket of nylon nano fiber and preparation method thereof |
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| CN105749339A CN105749339A (en) | 2016-07-13 |
| CN105749339B true CN105749339B (en) | 2019-01-15 |
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| CN110757922B (en) * | 2019-11-22 | 2023-08-01 | 厦门当盛新材料有限公司 | Composite fabric and production method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887365A (en) * | 2006-08-01 | 2007-01-03 | 四川大学 | Biological material film with porous structure and its prepn |
| CN104815355A (en) * | 2015-04-16 | 2015-08-05 | 四川大学 | Hydroxyapatite/polyamide composite biological material with nanofiber cellular structure on surface and preparing method thereof |
| CN105107022A (en) * | 2015-09-21 | 2015-12-02 | 东华大学 | Preparation method for nanofiber porous scaffold having compression elasticity in wet state |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030100944A1 (en) * | 2001-11-28 | 2003-05-29 | Olga Laksin | Vascular graft having a chemicaly bonded electrospun fibrous layer and method for making same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887365A (en) * | 2006-08-01 | 2007-01-03 | 四川大学 | Biological material film with porous structure and its prepn |
| CN104815355A (en) * | 2015-04-16 | 2015-08-05 | 四川大学 | Hydroxyapatite/polyamide composite biological material with nanofiber cellular structure on surface and preparing method thereof |
| CN105107022A (en) * | 2015-09-21 | 2015-12-02 | 东华大学 | Preparation method for nanofiber porous scaffold having compression elasticity in wet state |
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